Approximate singly excited states from a two-component Hartree-Fock reference

作者：Goings Joshua J^*; Ding Feizhi; Davidson Ernest R; Li Xiaosong

来源：Journal of Chemical Physics, 2015, 143(14): 144106.

DOI：10.1063/1.4932540

For many molecules, relaxing the spin symmetry constraint on the wave function results in the lowest energy mean-field solution. The two-component Hartree-Fock (2cHF) method relaxes all spin symmetry constraints, and the wave function is no longer an eigenfunction of the total spin, spin projection, or time-reversal symmetry operators. For ground state energies, 2cHF is a superior mean-field method for describing spin-frustrated molecules. For excited states, the utility of 2cHF is uncertain. Here, we implement the 2cHF extensions of two single-reference excited state methods, the two-component configuration interaction singles and time-dependent Hartree-Fock. We compare the results to the analogous methods based off of the unrestricted Hartree-Fock approximation, as well as the full configuration interaction for three small molecules with distinct 2cHF solutions, and discuss the nature of the 2cHF excited state solutions.

• 出版日期2015-10-14